HYMARC CORE ACTIVITY: CHARACTERIZATION - HYDROGEN.ENERGY.GOV
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HyMARC Core Activity: Characterization
Hydrogen Materials Advanced Research Consortium
Enabling twice the energy density for onboard H2 storage
Philip Parilla and David Prendergast
COVID-19 Pandemic halted all work in February 2020. Milestones to be evaluated after re-opening.
This presentation does not contain any proprietary, confidential, or otherwise restricted information
Project ID #: ST205
Overview
Timeline* Barriers addressed
Phase 1: 10/1/2015 to 9/30/2018 General:
Phase 2: 10/1/2018 to 9/30/2022 A. Cost, B. Weight and Volume, C. Efficiency,
E. Refueling Time
Project continuation determined
Reversible Solid-State Material:
annually by DOE. M. Hydrogen Capacity and Reversibility
(*previously a component of NREL’s N. Understanding of Hydrogen Physi- and Chemisorption
materials development program and O. Test Protocols and Evaluation Facilities
supported annually since 2006)
Budget Partners/Collaborators
DOE Budget (Entire HyMARC Team) NIST – Craig Brown, SLAC – Michael Toney
Total FY19: $4.3M HyMARC – SNL, LLNL, LBNL, PNNL team members
Total FY20 (Planned): $6.25M H2ST2, USA – Hydrogen Storage Tech Team
Colorado School of Mines - Colin Wolden, Brian
SNL: $1.15M Trewyn,
NREL: $1.5M (covers NIST and SLAC) Univ. Hawaii – Craig Jensen, Godwin Severa
PNNL: $1.1M Université de Genève – Hans-Rudolf Hagemann,
LLNL: $0.9M Angelina Gigante
LBNL (Long): $1.1M
LBNL (Prendergast) $0.5M
HyMARC Energy Materials Network: enhanced, highly coordinated
capabilities to accelerate materials discovery
• Foundational R&D
Enabling twice the energy density for hydrogen storage • Computational models
• Synthetic protocols
• Advanced characterization tools
• Validation of material performance
• Guidance to FOA projects
• Database development
Seedling Projects
• Applied material development
• Novel material concepts
• High-risk, high-reward
• Concept feasibility demonstration
• Advanced development of viable
concepts
3
Collaboration & Coordination: Seedling Seedlings: the HyMARC team assists individual projects with: • A designated HyMARC point-of-contact • Technical expertise concerning specific scientific problems • Access to HyMARC capabilities Ongoing • Development of Magnesium Boride Etherates as Hydrogen Storage Materials (U. Hawaii) • Electrolyte Assisted Hydrogen Storage Reactions (Liox Power) • ALD Synthesis of Novel Nanostructured Metal Borohydrides (NREL) • Optimized Hydrogen Adsorbents via Machine Learning & Crystal Engineering (U. MI) New • Optimal Adsorbents for Low-Cost Storage of Natural Gas and Hydrogen: Computational Identification, Experimental Demonstration, and System-Level Projection, U Mi • Developing A New Natural Gas Super-Absorbent Polymer (NG-SAP) for A Practical NG Storage System with Low Pressure, Ambient Temperature, and High Energy Density, PSU • Heteroatom-Modified and Compacted Zeolite-Templated Carbons for Gas Storage, MoSU • Theory-Guided Design and Discovery of Materials for Reversible Methane and Hydrogen Storage, Northwestern Methane and Hydrogen Storage with Porous Cage-Based Composite Materials, UD • Uniting Theory and Experiment to Deliver Flexible MOFs for Superior Methane or Hydrogen Storage, USF • Metal-Organic Frameworks Containing Frustrated Lewis Pairs for Hydrogen Storage at Ambient Temperature USF • Hydrogen Release from Concentrated Media with Reusable Catalysts, USC • A Reversible Liquid Hydrogen Carrier System Based on Ammonium Formate and Captured CO2, WSU • High Capacity Step-Shaped Hydrogen Adsorption in Robust, Pore-Gating Zeolitic Imidazolate Frameworks, Mines • Development of Magnesium Borane Containing Solutions of Furans and Pyrroles as Reversible Liquid Hydrogen Carriers, UH 4
Relevance: Hydrogen Storage Challenges
• The significant challenges associated with
practical and economical hydrogen storage
and transport require a collaborative national
research effort among the leading experts
and shared capabilities
• There are a myriad of plausible strategies for
improving hydrogen-storage technologies
that need to be investigated using state-of-
the-art characterization
• The goal is to Double hydrogen storage
energy density (increase from 25 to 50 g/L)
5
Relevance: NREL Characterization Activities
• Validate hydrogen capacity claims for DOE
– Measure “champion” samples from DOE grant awardees
• Promote valid comparisons of hydrogen-storage materials
and decrease irreproducibility due to errors
– Provide uniform and well-defined metrics for comparisons
– Understand sources of common errors and how to mitigate them
– Promote volumetric capacity protocols
• Conduct inter-laboratory comparison for capacity
measurements
– Analyze actual implementations of protocols and variations thereof
– Provide feedback to participants on errors and discrepancies
• Provide variable-temperature PCT measurements
• Provide in-situ thermal conductivity measurements
• Provide TPD & DRIFTS measurements
6
Approach: NREL Characterization Activities
• New PCT Evaluation
- Review of quality for commercial PCT instrumentation
• Improvements to CryoPCT
- Better temperature control & minimized residual torsion on
sample holder
• Progress on Qst Analysis
- Additional analysis & publish paper
• Protocol development for expansive materials
- How is capacity determination affected?
• DRIFTS & Synchrotron measurements
- Seedling support
• Thermal Conductivity measurements
• Variable-temperature PCT measurements
• TPD & DRIFTS measurements 7
NREL Characterization Accomplishments
• New PCT Evaluation
- Extensive investigation into current PCT instruments
- Four main OEM: Setaram, Micromeritics, Anton Paar, Hiden
- Mole-balance models, null measurements, & RR sample
- Significant instrumental and operator issues for RR measurements
- Setaram did NOT participate in RR sample (do not have testing capabilities)
Excess Gravimetric Capacity 4 Excess Gravimetric Capacity Thick line = median
0.5 Liquid N2 Temperature Upper box limit = 75% quartile
Ambient Temperature Lower box limit = 25% quartile
Whiskers at 10% & 90%
Mean
RR-2019 Hiden
Hydrogen Uptake/ wt%
Hydrogen Uptake/ wt%
Anton Paar
0.4 results are 3 Anton Paar Corr
Anton Paar Redo
shown in gray Micromeritics
0.3
2
Thick line = median
0.2 Upper box limit = 75% quartile
Lower box limit = 25% quartile RR-2019
Whiskers at 10% & 90%
Mean results are
1
Hiden shown in gray
0.1 Anton Paar
Anton Paar Corr
Micromeritics
0
0.0
-20 0 20 40 60 80 100 120 0 20 40 60 80 100 120 140
Pressure/ bar Pressure/ bar
8
NREL Characterization Accomplishments
• Improvements to CryoPCT
- Hardware modifications allow:
o More uniform, stable, and reproducible temperature profiles
o Minimizes residual torsional stress on sample holder
- Master Calibrations are in Progress
Before After
9
Progress on Isosteric Heat Analysis: Noise Sensitivity
• This data is generated from an 250
Histogram of Equilibrium Constants from Simulations
Relative Gaussian Noise on Isotherm Data
idealized Langmuir model with Qst =
Langmuir with Energy = 7 kJ/mole
273 K; 5% Noise
200 273 K; 1% Noise
293 K; 5% Noise
Histogram Count
7 kJ/mole at 273 & 293 K.
293 K; 1% Noise
150
• Various noise levels added to the 100
isotherms cause fits to the isotherms
50
to not have the true values.
0
• Using these imperfect fits to 0.14 0.16 0.18 0.20
Equilibrium Constant from Fit
0.22 0.24 0.26
determine Qst then cause errors in 5
10
Qst. Langmuir
7 kJ/mole actual
T = 273 K & 293 K
• In this example, for a given noise
4
10 5.0% noise
Histogram Counts
1.0% noise
level ‘�%’, the resulting noise % level 0.1% noise
in Qst is ~6n�, where n is the # of std.
3
10
dev.
2
10
• For �=5% noise, it is quite probable
to get 60% error in Qst (n=2). 1
10
0 2 4 6 8 10 12 14 16
Calculated Qst (kJ/mole)
10Advanced Characterization @ LBNL
Sandia Contributors: White, El Gabaly Ambient Pressure XPS (Sandia)
Stavila, Allendorf
Interpretation of near-surface XPS
Synchrotron AP-XPS
ALS BL 11.0.2
White et al., ACS Appl. Mater. Interfaces 11, 4930 (2019)
LLNL Collaborators:
Lab-based AP-XPS Rowberg, Wan,
Sandia Kang, WoodAdvanced Characterization @ LBNL Yi-Sheng Liu
In situ/Operando Soft X-ray Spectroscopy Jinghua Guo
Simulation of Interfaces and their X-ray Spectra
Pragya Verma
David Prendergast
hydrogenation 1bar, RT- 250°C
TFY (um), TEY (nm)
750 K
H2 release, RT- 500°C
TFY (um), TEY (nm) New H2 reaction cell for soft x-rays: 1000 K
• H2 pressure: up to 5 barOperando Soft X-Ray Characterization
Techniques
Yi-Sheng Liu
100 nm Si3N4 Jinghua Guo Nature 2008, 456, 222
membrane
Fluo
r
(FY) escenc 20 nm Pt film
e
hv
EY e-
Operando XAS/RIXS Operando STXM
Knowledge of the structure and composition Microscopy platform for imaging nanoscale changes
of nanometer-thin solid-gas interface regions inside hydride particles, which provides new insights
is key for understanding H2-adsorption/- about performance and adsorption/desorption that
desorption phenomena could improve hydrogen storageStructure characterization capabilities Yi-Sheng Liu
Jinghua Guo
Transmission SAXS/WAXS
In situ and operando high temperature
X-ray powder diffraction in variable
gaseous environments
Grazing incidence SAXS/WAXS
GIWAXS
GISAXS
Detector
αf
αf
Sampl ● Temperatures in excess of 1100°C, controlled
e ramp rates in excess of 100°C/min
αi ● Controlled gas environments from mTorr to ~2atm
● In-situ and in-operando time resolved studies
thin films on substrate
(20 - 100 nm thick)Advanced Characterization Capabilities
(4.C: NMR Spectroscopy)
High Pressure NMR Capability
• New rotors for high pressure
NMR
• 1-way valve for sequential
addition of gas to sealed rotor
• 200 bar pressure
• -20 to + 50 °C, greater
temperature range being
developed
• Static or magic-angle spinning
• Greater control of sample
inside detection coils
• 10 rotors prepared for Design of rotors to allow 1-way gas
HyMARC researchers to load at addition (left); and rotors and tools
their laboratories under construction in the EMSL
workshop (top).
• Minimizes contamination
during loading
• Toolset for loading and
unloading can be distributed
15Advanced Characterization Capabilities
(4.C: NMR Spectroscopy)
Seedling Support: MAS-NMR of ALD-coated Mg(BH4)2
• Use of high-pressure NMR rotors to study dehydrogenation in situ of Mg(BH4)2
coated with BN, TiN
• H2 observed at 100 °C when using “wet” N2H4 in the ALD process (not “dry”)
• New boron signal at ca. +20 ppm correlated with H2 generation
• Strongest for 10 BN /100 TiN layers
Noemi Leick - NREL 16Advanced Characterization Capabilities
(4.B: PCT CALORIMETRY)
Simultaneous determination of the adsorption isotherm and
the adsorption enthalpy
• We are developing a
microcalorimetric setup capable of
measuring isotherm and enthalpy
directly at sub-ambient conditions
• Currently differential enthalpy
calculated using Clausius–Clapeyron
equation
• Combining a low temperature
Calvet-Tian calorimeter with a PCT
as a microdoser
• Capable of measuring adsorption
isotherm and enthalpy at 77K and
above
References:
L. Llewellyn et al., C. R. Chimie 8 (2005).
JA Mason et al. Nature 1-15 (2015)
doi:10.1038/nature15732
Low Temperature Calorimeter (from B. Schmitz et al, ChemPhysChem, Volume 9, Issue 15,
-196°C to 200°C (BT2.15) pages 2181–2184 (2008) 17Reaction calorimetry: direct measure of
heat of triazine hydrogenation
+ heat
First experiments. Measurement of enthalpy of H2 uptake by
triazine. ΔH =36 or 54 kJ/mol H2?
Campbell, Abbey,
Neiner, Grant,
Dixon, Liu
J. AM. CHEM.
Heat of hydrogenation of CBN
SOC. 2010, 132,
18048
18New Spectrometer Design
Cryostat & sample
Bruker Vertex70 FTIR
Spectrometer
Range (MCT) 8,000–650 cm –1
Resolution 0.4 cm –1
Temperature Control
High Temperature Cell 35–180 °C
Low Temperature Cell 300–15 K
Pressure Control
ASAP2020Plus 0–1 bar
External optics
& detector HPVA II* 0–120 bar
* Coming soon
• Custom design improving on previous setups
• External optical path allows modularity
• Many different temperature/pressure options available
19In Situ Gas Dosing Variable Temperature FTIR
Cryostat
Sample
rod Gas adsorption
analyzer
Spectrometer Gas dosing
manifold
DRIFTS module
• Custom design improving on previous setups
• External optical path allows modularity
• Many different temperature/pressure options available
20Tracking Individual Adsorption Sites
77 K 77 K
― Site 2 fit (2-site
Langmuir)
+ IR peak 2 area
● Total H2 uptake
― Site 1 fit (2-site
Langmuir)
+ IR peak 1 area
• Integrating area under IR peak allows site-specific
quantification
21Variable Temperature & High-Pressure IR
First site
Free H2 4030 cm–1
4152 cm–1
Second site
4130 cm–1
−ΔH° = 13.6 kJ/mol
−ΔS° = 85 J/mol·K
4100 4150 4000 4200 4100 4000
• Van’t Hoff relation allows determination of site-specific thermodynamics
• Comparable with zero coverage Qst
• Manifold was pressurised with H2 up to 100 bar and both sites
observed at higher pressures
22R&D of Advanced Characterization Core
Capabilities at SLAC
Nichrome Heaters: Pressure-resolved
20–800°C measurements
Next steps:
NREL Variable Pressure Gas Manifold:
Design and 3D print “dark Pmax = ~100 bar, Pmin = ~10-7 mbar
Oxford Cryostream: cell” enclosure for pulsed
90 – 298 K optical experiments
(HyMARC plasmon projects)
Heating option
Static or variable pressure option
Cooling option
Next steps:
Interfacing PCT system with the in-situ
scattering cell
Currently in progress: (HyMARC sorbent, hydrides projects)
New sample cell mounted in CCR with gas
dosing capabilities, lower Tmin to ~10 K Compatible with a variety of
(HyMARC sorbent projects)
techniques
• X-ray diffraction (XRD)
• Capillary sample holder options: Capillary sample cell mounted at SSRL BL 2-1 • Small angle x-ray scattering (SAXS)
• High-purity quartz, 0.2 mm thick Tmelt= • X-ray pair distribution function
Anton Paar DHS 900 domed hot analysis (PDF)
~1700°C, Pmax = ~130 bar @ RT) stage (i.e. flat plate geometry) • X-ray Raman spectroscopy (XRS)
• Single crystal sapphire, 0.4mm thick also available
Tmelt = ~2300°C, Pmax = ~550 • X-ray absorption spectroscopy (XAS)
bar@RT)
• Kapton (polyimide) Nicholas Allan Strange
Michael ToneyR&D of Advanced Characterization Core
Capabilities at SLAC
Hydrides: FA 2.D.2 Non-innocent hosts for MH Hydrogen Carriers: FA 3.C Eutectic Systems
encapsulation (SNL – Stavila) and Hydrogen Carriers (NREL – Bell)
SAXS suggests the LAH and N-CMK3 β-Mg(BH4)2 + (CH3)4NBH4
domains remain fixed in size with
increasing temperature. N-doping Physical mixture results in new phase (possible
appears to potentially stabilize a eutectic) formation around ~175°C
reversible intermediate
Phase melts around 200°C and migrates away
WAXS from heat source (see inset)
SAXS 200 °C
Intensity (a.u.)
175 °C
100 °C
20 °C
8 10 12 14 16 18 20 22
2q (l = 0.729 Å)
SAXS/WAXS on
LiAlH4 nanoconfined
in N-doped CMK-3
mesoporous carbonResearch Support for HyMARC Seedling
Support (NREL-Christensen)
100c N2H4 + BBr3 on γ-Mg(BH4)2 100c Al2(CH3)6 on γ-Mg(BH4)2
Temperature-resolved XRD shows N2H5Br in the
room temperature product. The hydrazinium SAXS In situ SAXS suggests
species melts around 90°C shortly followed by the pore structure
formation of MgBr2 and rapid H2 release originating from γ-
Mg(BH4)2 is retained
with increasing
temperature
WAXS
WAXS shows the TMA-
MBH sample forms
III MgH2 and Mg nearly
100 °C lower than
II the neat borohydride
Nicholas Allan Strange
Michael Toney IH2 Storage Characterization and Craig Brown
Optimization Research Effort Ryan Klein
Chemically bound
Provide information about
- where the ‘H’ is
- How is it bound/adsorbed
- How it moves
INS & DFT of Mg(BH4)2
Polymorphs (w\ SANDIA)
Chemically bound
MolecularProposed Future Work • Assist the seedling projects by using HyMARC’s unique characterization capabilities • Apply the same characterization capabilities to HyMARC’s internal materials-research programs • Publish findings using state-of-the-art and unique characterization capabilities to investigate new hydrogen storage and carrier materials • Develop new and improve existing characterization capabilities to enhance understanding and optimization of hydrogen storage and carrier materials Any proposed future work is subject to change based on funding levels. 27
Summary
• The significant challenges associated with practical and economical
hydrogen storage and transport require a collaborative national
research effort among the leading experts and shared capabilities
• Many of these capabilities exist at national user facilities at ALS,
NIST, PNNL, & SLAC
• Activities include these characterization capabilities:
o Calorimetry o SAXS
o In-situ DRIFTS o Operando STXM
o In-situ FTIR o TPD
o INS o WAXS
o In-situ NMR o XAS
o PCT o Operando XPS
o PCT calorimetry o In-situ XRD
o In-situ Thermal o X-ray PDF
Conductivity o XRS
28Contributors
• LBNL • NREL • SLAC
– J Guo – RT Bell – NA Strange
– YS Liu – ST Christensen – MF Toney
– JR Long – T Gennett • SNL
– P Verma
– KE Hurst – MD Allendorf
• LLNL – N Leick – F El Gabaly
– S Kang
– R Mow – V Stavila
– AJE Rowberg
– S Shulda – JL White
– LF Wan
– BC Wood • PNNL
• NIST – T Autrey
– CM Brown – ME Bowden
– RA Klein – K Grubel
– AJ Karkamkar 29We are grateful for the financial support of EERE/HFTO and
for technical and programmatic guidance from
Ned Stetson, Jesse Adams, and Zeric Hulvey
Hydrogen Materials Advanced Research Consortium
Enabling twice the energy density for onboard H2 storage
30Tech Back Up Slides
31A Responses to Previous Year Reviewers’ Comments
This project was not reviewed last year.
32Temperature Programmed Desorption
• Sample is heated in
high vacuum at a
constant rate
• 77 K < T < 1500 K
• Molecular effluents
are monitored vs T
with the mass spec.
• Can detect any
volatile adsorbed
species
• Can be calibrated to
measure H2 capacity
• Provides activation
energy and order of
Diagram of TPD apparatus desorption
General Reference: R.J. Madix, Chemistry and Physics of
Solid Surfaces, Volume II, ed. R. Vanselov, CRC, Boca
33
Raton, (1979) 63-72Cryo DRIFTS Capability
• In-situ DRIFTS
High temperature reaction chamber suitable
for studies at controlled temperatures (up to
1183 K) and pressures (up to 34 bar)
• High pressure dome and ZnSe windows
• Three inlet/outlet ports for evacuating the cell and
introducing gases
Low temperature reaction chamber suitable for
studies at variable temperatures (123 K to 873 K)
and pressures (up to 1.3 bar)
• Attached dewar cooled with liquid nitrogen
* Chambers are used in conjunction with the Praying
Mantis diffuse reflectance accessory (Harrick)
34DSC/TGA/MS/GC
• Simultaneous TG-DSC coupled with a
mass-spec
• Additional capabilities to couple with FTIR
or GC
• -150 to1000 ℃ temperature range with
controlled atmosphere
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